Effect of Calcination and Reduction Temperatures on the Reduction and Activity of Boron-modified Co/TiO2 Fischer-Tropsch Catalys

The effect of calcination and reduction temperatures on the reducibility, dispersion and Fischer-Tropsch activity of 10 wt% cobalt supported on titania catalyst modified by 0.1 wt% boron has been studied. The percentage reduction and percentage dispersion were found to decrease with increasing calcination temperature. The higher calcination temperatures decreased the total CO hydrogenation activity, but did not affect the turnover frequency. The decrease in CO hydrogenation rate with increasing calcination temperature is attributed to a decrease in the number of surface active sites. The higher reduction temperature also decreased the total activity. This may be due to the loss of the surface active sites, caused by blocking of the TiOc phases produced at higher reduction temperatures. The higher calcination temperature shifted the F-T product spectrum to the lower weight hydrocarbons. The reduction temperature did not affect the product selectivity. South African Journal of Chemistry Vol.57 2004: 49-5

Effect of Cobalt Source on the Catalyst Reducibility and Activity of Boron-modified Co / TiO2 Fischer-Tropsch Catalysts

The effect of cobalt precursor (nitrate, acetate and chloride salts) on the catalyst reducibility and dispersion, as well as the catalytic activity of the Fischer-Tropsch (FT) synthesis, of boron-modified titania-supported cobalt catalysts (0.1%B/10%Co/TiO2) has been investigated. FT studies were performed on both calcined and uncalcined catalysts prepared from the three cobalt sources. The uncalcined nitrate catalyst showed a higher activity for FT synthesis compared to the uncalcined acetate and chloride catalysts. For the calcined catalysts, the acetate and nitrate catalysts exhibited higher FT activity. The low activity associated with the chloride catalyst related to poisoning by residual chloride ions. Calcination was found to enhance the extent of cobalt bulk reduction and FT activity for all three of the catalysts. The FT reaction rate increased with increasing percentage cobalt dispersion while the turnover frequency (TOF) was found be near independent of cobalt source. South African Journal of Chemistry Vol.56 2003: 1-

IN SITU AND POST REACTION COBALT-INCORPORATION INTO AMINOPROPYL-MODIFIED PERIODIC MESOPOROUS ORGANOSILICA MATERIALS

Bifunctional periodic mesoporous organosilica materials with and without cobalt ion incorporation were synthesized by co-condensation of 1,2-bistrimethoxysilylethane (BTME) with 3-aminopropyltriethoxysilane (APTS) in the presence of cetyltrimethylammonium bromide. Cobalt was incorporated onto APTS-modified ethylene-bridged silica materials by in situ and by incipient wetness addition methods. The periodicity of the new materials is indicated by the presence of low angle diffraction peaks found in the XRD profiles (pore size ca. 40 nm). The surface area, pore volume and pore diameter of the new ethylene-bridged silica materials decreased with increasing loading of APTS as well as after cobalt incorporation. Thermogravimetric analysis and Raman spectroscopy show that the surfactant is removed by solvent extraction. Cobalt ion incorporation is confirmed by Raman spectroscopy and UV-vis diffuse reflectance spectroscopy. KEY WORDS: Bifunctional periodic mesoporous organosilica, 1,2-bistrimethoxysilylethane, 3-aminopropyltriethoxysilane, Sol-gel, Cobalt Bull. Chem. Soc. Ethiop. 2005, 19(2), 197-212

The Synthesis of Carbon Nanomaterials using Chlorinated Hydrocarbons over a Fe-Co/CaCO3 Catalyst

The effect of chlorine on the morphology of carbon nanotubes (CNTs) prepared from a Fe-Co/CaCO3 catalyst was investigated using chlorobenzene (CB), dichlorobenzene (DCB), trichlorobenzene (TCB), dichloroethane (DCE), trichloroethane (TCE) and tetrachloroethane (TTCE) as chlorine sources using a catalytic chemical vapour deposition (CCVD) method. Toluene was used as a chlorine-free carbon source for comparison. Multi-walled carbon nanotubes (MWCNTs) were successfully synthesized. The physicochemical properties of the CNTs were studied using transmission electron microscopy (TEM), Raman spectroscopy, thermal gravimetric analysis (TGA), energy-dispersive X-ray spectroscopy (EDS), powder X-ray diffraction (PXRD) spectroscopy, and X-ray photoelectron spectroscopy (XPS) techniques. The inner and outer diameters of the MWCNTs increased with an increase in the number of chlorine atoms contained in the reactant. Chlorine incorporation into the MWCNTs was observed by EDS analysis for all reactants. Formation of ‘bamboo-like’ structures for the MWCNTs generated from TCE and TTCE was also observed, facilitated by the presence of the high percentage of chlorine in these reactants. Numerous MWCNTs revealed the presence of small carbon nanostructures that grew on top of the dominant CNTs, suggesting an unexpected secondary carbon growth mechanism.KEYWORDS Multi-walled carbon nanotubes, CVD, synthesis, chlorine, benzenes, ethanes

A review of shaped carbon nanomaterials

Materials made of carbon that can be synthesised and characterised at the nano level have become a mainstay in the nanotechnology arena. These carbon materials can have a remarkable range of morphologies. They can have structures that are either hollow or filled and can take many shapes, as evidenced by the well-documented families of fullerenes and carbon nanotubes. However, these are but two of the shapes that carbon can form at the nano level. In this review we outline the types of shaped carbons that can be produced by simple synthetic procedures, focusing on spheres, tubes or fibres, and helices. Their mechanisms of formation and uses are also described

Microwave treatment: a facile method for the solid state modification of potassium-promoted iron on silica Fischer-Tropsch catalysts

Potassium-promoted (0–1.5 wt%) iron–silica catalysts for Fischer–Tropsch synthesis (FTS) have been modified using microwave radiation. Radiation produced few or no modifications in the bulk properties, but surface and catalytic behaviour were markedly changed in K promoted 10 wt% of Fe/SiO2 (10Fe/SiO2) catalysts. The effect of potassium on CO adsorption was relatively insignificant in untreated catalysts, but was large in microwave-modified catalysts. Radiation induced an increase in CH4 formation in CO + H2 temperature programmed surface reactions. Microwave treatment promoted CH4 formation from graphitic carbon in these catalysts, while decreasing CH4 formation from α- and β-carbon species, and overall favoured strong CO adsorption onto the catalyst surface. Microwave effects were catalyst particle size and treatment duration-dependent. At low alkali concentration, microwaved samples showed improved ethene selectivities, higher alpha values and lower methane and light alkene selectivities. When 0.7 wt% K was added to the 10Fe/SiO2 catalyst, the α value increased from 0.59 to 0.66 after treatment of the sample with microwave radiation in the solid state

Origin of conductivity cross over in entangled multi-walled carbon nanotube network filled by iron

A realistic transport model showing the interplay of the hopping transport between the outer shells of iron filled entangled multi-walled carbon nanotubes (MWNT) and the diffusive transport through the inner part of the tubes, as a function of the filling percentage, is developed. This model is based on low-temperature electrical resistivity and magneto-resistance (MR) measurements. The conductivity at low temperatures showed a crossover from Efros-Shklovski (E-S) variable range hopping (VRH) to Mott VRH in 3 dimensions (3D) between the neighboring tubes as the iron weight percentage is increased from 11% to 19% in the MWNTs. The MR in the hopping regime is strongly dependent on temperature as well as magnetic field and shows both positive and negative signs, which are discussed in terms of wave function shrinkage and quantum interference effects, respectively. A further increase of the iron percentage from 19% to 31% gives a conductivity crossover from Mott VRH to 3D weak localization (WL). This change is ascribed to the formation of long iron nanowires at the core of the nanotubes, which yields a long dephasing length (e.g. 30 nm) at the lowest measured temperature. Although the overall transport in this network is described by a 3D WL model, the weak temperature dependence of inelastic scattering length expressed as L_phi ~T^-0.3 suggests the possibility for the presence of one-dimensional channels in the network due to the formation of long Fe nanowires inside the tubes, which might introduce an alignment in the random structure.Comment: 29 pages,10 figures, 2 tables, submitted to Phys. Rev.

Deciphering the structural, textural, and electrochemical properties of activated BN-doped spherical carbons

In this study, the effect of K2CO3 activation on the structural, textural, and electrochemical properties of carbon spheres (CSs) and boron and nitrogen co-doped carbon spheres (BN-CSs) was evaluated. Activation of the CSs and BN-CSs by K2CO3 resulted in increased specific surface areas and ID/IG ratios. From the X-ray photoelectron spectroscopy (XPS) results, the BN-CSs comprised of 64% pyridinic-N, 24% pyrrolic-N and 7% graphitic-N whereas the activated BN-CSs had 19% pyridinic-N, 40% pyrrolic-N and 22% graphitic-N displaying the effect of activation on the type of N configurations in BN-CSs. A possible BN-co-doping and activation mechanism for the BN-CSs is proposed. Electrochemical analysis of the electrode materials revealed that BN doping, carbon morphology, structure, and porosity played a crucial role in enhancing the capacitive behavior of the CSs. As a proof of concept, a symmetric device comprising the activated BN-CSs displayed a specific power of 800 W kg 1 at a specific current of 1 A g 1 within an operating cell potential of 1.6 V in a 3 M KNO3 electrolyte. The study illustrated for the first time the role of K2CO3 activation in influencing the physical and surface properties of template-free activated BN-CSs as potential electrode materials for energy storage systems.The South African Research Chairs Initiative of the Department of Science and Technology and the National Research Foundation of South Africa (Grant No. 61056). B.K.M. and B.J.M. would like to thank the University of the Witwatersrand and the DST-NRF Centre of Excellence in Strong Materials (CoESM) for financial support. B.K.M. would also like to acknowledge financial support from the NRF and the University of Pretoria for her postdoctoral fellowship grant.http://www.mdpi.com/journal/nanomaterialsam2019Physic

Post doped nitrogen-decorated hollow carbon spheres as a support for Co Fischer-Tropsch catalysts

In this study the outer surface of porous hollow carbon spheres (HCSs) materials were functionalized by N-doping using a post-synthesis method and they were used as a Fischer-Tropsch catalyst support. Melamine was used as the nitrogen source, and carbonization was performed at different temperatures (600 and 900 °C) to introduce variable levels of N into the HCSs, with different bonding configurations. This procedure allowed for the incorporation of up to 13% N. Our results show that post-synthesis N-doping introduced marginal defects into the carbon framework and this did not affect the thermal stability of the materials. XPS studies revealed that the surface content on these materials varied and provided evidence for temperature-tunable bonding configurations. Effects associated with post-synthesis N-doping were apparent on the Co catalyst (˜10 wt.%) properties such as the inhibited reduction caused by a metal-support interaction observed by the H2-TPR and in situ PXRD techniques. As a consequence the Fischer-Tropsch performance was influenced as both the activity and stability were improved on the catalysts supported on the N-doped materials. TEM analysis of the spent catalysts demonstrated the influence of N-doping on the sintering characteristics of Co, with particles > 30 nm measured on the N-free catalyst while N-doped samples had sizes < 15 nm

Effect of a titania covering on CNTS as support for the Ru catalysed selective CO methanation

One of the major set-backs in the selective CO methanation process, as the final clean-up step in removing residual CO from reformate gas feed, is the reverse water gas shift (RWGS) reaction. This reaction is an undesired reaction because, it runs parallel with the selective CO methanation reaction. This increases the CO outlet concentration. The catalytic performance of ruthenium supported on carbon nanotubes (CNTs), nitrogen doped carbon nanotubes (NCNTs), titania coated carbon nanotubes (NCNT-TiO2 and CNTs-TiO2) and TiO2 anatase (TiO2-A) for selective CO methanation was investigated. The feed composition relevant to reformate gas was used but in the absence of steam. The experiments were conducted within a temperature range of 100 °C and 360 °C. It was observed that carbon dioxide methanation was suppressed until CO methanation attained a maximum conversion for all the catalysts studied. The Ru/NCNT showed higher activity than Ru/CNT at all temperatures examined due to the nitrogen incorporation in the carbon domains. Both Ru/CNT and Ru/NCNT however promoted the RWGS reaction at temperatures above 250 °C. The Ru/CNT-TiO2 catalyst recorded the highest activity for both the CO and selective CO methanation followed by Ru/TiO2-A. The presence of titania on the carbon nanotubes significantly retarded the RWGS reaction from about −120% CO conversion to about 80% CO conversion, while selectivity towards methane increased in all catalysts with increasing temperature